Enhancer composition for agricultural chemicals and agricultural chemical composition

ABSTRACT

An enhancer composition for agricultural chemicals which can enhance the effectiveness of an agricultural chemical without causing any phytotoxicity to various crops, which comprises at least one nitrogen-containing compound selected from the group consisting of a tertiary amine, a tertiary amine salt and a quaternary ammonium salt and a chelating agent, wherein the content of the chelating agent ranges from 0.01 to 30 mol per mol of the nitrogen-containing compound.

This application is a continuation of application Ser. No. 08/507,483,filed on Aug. 28, 1995, now abandoned application Ser. No. 08/507,483 isthe national phase of PCT International Application No. PCT/JP94/02263filed on Dec. 27, 1994 under 35 U.S.C. §371. The entire contents of eachof the above identified applications are hereby incorporated byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an enhancer composition foragricultural chemicals, an agricultural chemical composition, a methodfor enhancing the effectiveness of an agricultural chemical, a use ofthe above-mentioned enhancer composition for agricultural chemicals forthe preparation of an agricultural chemical composition, a use of theabove-mentioned enhancer composition for agricultural chemicals forenhancing the effectiveness of an agricultural chemical and anagricultural chemical kit.

2. Description of the Related Art

Agricultural chemicals including insecticides, fungicides (orbactericides), herbicides, miticides (or acaricides) and plant growthregulators have been used in the forms of, for example, emulsions,wettable powders, granules, powders and flowables. In the properties ofthese agricultural chemical preparations, various attempts have beenmade to achieve the maximum effectiveness of the agricultural chemicals.However, it has been difficult to enhance the effectiveness ofagricultural chemicals through adjustments in formulations. It isfurther difficult to develop novel agricultural chemicals. Therefore,further enhancement of existing agricultural chemicals would highlycontribute to the industry.

As substances capable of enhancing the effectiveness of agriculturalchemicals, surfactants comprising various nitrogen-containing compoundssuch as quaternary ammonium salts, betaines and amine oxides have beenknown (see European Patent Publication-A No. 274369, published on Jul.13, 1988). It is known that quaternized or further polyoxyethylenatedlong-chain amines, among the above-mentioned compounds, are effectivefor this purpose. However, the enhancement effect of the above describedcompounds capable of enhancing the effectiveness of agriculturalchemicals is not always satisfied.

Since an agricultural chemical is diluted with water prior to use, itcontains a chelating agent for trapping metal ions, etc., existing inthe water. For example, European Patent Publication-A No. 36106(published on Sep. 23, 1981) has disclosed a herbicide compositioncomprising a phosphinothricin derivative, a specific quaternary ammoniumsalt and a chelating agent. However, particular examples of thequaternary ammonium salts disclosed in this patent include ammoniumsulfate, ammonium nitrate, ammonium acetate and the like, and do notinclude organic quaternary ammonium salts generally used as cationicsurfactants. Further, Japanese Patent Publication-A No. 55-98105(published on Jul. 25, 1980) has disclosed a herbicide compositioncomprising a bisphosphonic acid herbicide and a chelating agent.However, this patent does not suggest the combination use of an organicquaternary ammonium salt as a cationic surfactant and a chelating agent.

DISCLOSURE OF THE INVENTION SUMMARY OF THE INVENTION

From a standpoint that the efficacy of an agricultural chemical can beenhanced by using the agricultural chemical together with at least onenitrogen-containing compound selected from the group consisting of atertiary amine, a tertiary amine salt and a quaternary ammonium salt,the present inventors have conducted extensive studies. As a result,they have found that the efficacies of various agricultural chemicalscan be remarkably enhanced by adding a nitrogen-containing compoundtogether with a chelating agent thereto. The present invention has beencompleted on the basis of this finding.

Thus, the present invention provides an enhancer composition foragricultural chemicals comprising at least one nitrogen-containingcompound selected from the group consisting of a tertiary amine, atertiary amine salt and a quaternary ammonium salt and a chelatingagent, wherein the content of the chelating agent ranges from 0.01 to 30mol per mol of the nitrogen-containing compound. The nitrogen-containingcompound is preferably a nitrogen-containing surfactant selected fromthe group consisting of an organic tertiary amine, an organic tertiaryamine salt and an organic quaternary ammonium salt.

Further, the present invention provides an agricultural chemicalcomposition comprising an agricultural chemical, at least onenitrogen-containing compound selected from the group consisting of atertiary amine, a tertiary amine salt and a quaternary ammonium salt anda chelating agent, wherein the content of the chelating agent rangesfrom 0.01 to 30 mol per mol of the nitrogen-containing compound and theweight ratio of the total of the nitrogen-containing compound and thechelating agent to the agricultural chemical ranges from 0.05 to 50.

Furthermore, the present invention provides a method for enhancing theeffectiveness of an agricultural chemical which comprises applying theabove-mentioned enhancer composition for agricultural chemicals with anagricultural chemical to a locus which would be benefit from suchtreatment, a use of the above-mentioned enhancer composition foragricultural chemicals for the preparation of an agricultural chemicalcomposition, and a use of the above-mentioned enhancer composition foragricultural chemicals for enhancing the effectiveness of anagricultural chemical.

In addition, the present invention provides an agricultural chemical kitwhich comprises a container containing the above-mentioned enhancercomposition for agricultural chemicals and a container containing anagricultural chemical composition, an agricultural chemical kit whichcomprises a container containing the above-mentioned enhancercomposition for agricultural chemicals, a container containing asurfactant other than the above nitrogen-containing compounds and acontainer containing an agricultural chemical composition, anagricultural chemical kit which comprises a container containing theabove-mentioned enhancer composition for agricultural chemicals, acontainer containing an adjuvant for penetration of agriculturalchemicals and a container containing an agricultural chemicalcomposition, and an agricultural chemical kit which comprises acontainer containing the above-mentioned enhancer composition foragricultural chemicals, a container containing a surfactant other thanthe above nitrogen-containing compounds, a container containing anadjuvant for penetration of agricultural chemicals and a containercontaining an agricultural chemical composition.

In this specification, the term “agricultural chemical” means one whichis employed as an active or principle ingredient in common agriculturalchemical compositions or preparations, and examples thereof include afungicide (or a bactericide), an insecticide, a miticide (or anacaricide), a herbicide, a plant growth regulator and the like.

Further the scope and the applicability of the present invention willbecome apparent from the detailed description given hereinafter.However, it should be understood that the detailed description andspecific examples which follow, while indicating preferred embodimentsof the invention, are given by way of illustration only, since variouschanges and modifications within the spirit and scope of the inventionwill become apparent to those skilled in the art from this detaileddescription.

DETAILED DESCRIPTION OF THE INVENTION

[I] Nitrogen-containing compound (A)

Among compounds to be employed as a nitrogen-containing compound in thepresent invention, examples of the organic tertiary amine include thosewhich will be described below.

(1) Amines represented by the following formula (1):

wherein R¹ represents a linear or branched alkyl or alkenyl group having8 to 22 carbon atoms; each A represents an alkylene group, preferably analkylene group having 2 to 4 carbon atoms; n and m each represents sucha number that the sum of n and m, i.e., the average oxyalkylene numberper molecule, is 1 to 40, generally an integer; and R² and R³ are thesame or different from each other and each represents a hydrogen atom oran acyl group (for example, formyl group, acetyl group, propionyl groupor benzoyl group).

(2) Amines represented by the following formula (2):

wherein R¹ and R² are the same or different from each other and eachrepresents an alkyl group having 1 to 4 carbon atoms which may besubstituted by a hydroxyl group, preferably an alkyl group having 1 to 4carbon atoms; R³ and R⁴ are the same or different from each other andeach represents a linear or branched alkyl or alkenyl group having 4 to36 carbon atoms which may be substituted by a hydroxyl group; each R⁵represents a hydrogen atom or a methyl group; each R⁶ represents ahydrogen atom or a methyl group; m and n are the same or different fromeach other and each represents a positive number of 1 to 5; and p and q,which generally each represents an average value, are either the same ordifferent from each other and each represents a number of 0 to 30.

(3) Amines represented by the following formula (3):

wherein R¹ represents an alkyl group having 1 to 4 carbon atoms whichmay be substituted by a hydroxyl group; R² represents a linear orbranched alkyl group having 1 to 36 carbon atoms which may besubstituted by a hydroxyl group or a linear or branched alkenyl grouphaving 2 to 36 carbon atoms which may be substituted by a hydroxylgroup, preferably a linear or branched alkyl or alkenyl group having 5to 36 carbon atoms which may be substituted by a hydroxyl group, a grouprepresented by the formula: —C_(n)H_(2n)—(G¹)—R⁴ (wherein R⁴ representsa linear or branched alkyl or alkenyl group having 5 to 36 carbon atomswhich may be substituted by a hydroxyl group; G¹ represents a grouprepresented by the formula: —OCO— or a group represented by the formula:—NHCO—; and n represents a positive number of 2 to 6), a grouprepresented by the formula:

(wherein R⁵ represents a linear or branched alkyl or alkenyl grouphaving 6 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R⁶ represents a hydrogen atom or a methyl group; m is apositive number of 1 to 5; and p, which generally represents an averagevalue, is a number of 0 to 30) or a group represented by the formula:

(wherein R⁷ represents a linear or branched alkyl or alkenyl grouphaving 4 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R⁸ represents a hydrogen atom or a methyl group; G²represents a group represented by the formula: —OCO— or a grouprepresented by the formula: —NHCO—; i represents a positive number of 2to 6; k represents a positive number of 1 to 5; and q, which generallyrepresents an average value, represents a number of 0 to 30; and R³represents a group represented by the formula:

(wherein R⁹ represents a linear or branched alkyl or alkenyl grouphaving 4 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R¹⁰ represents a hydrogen atom or a methyl group; G³represents a group represented by the formula: —OCO— or a grouprepresented by the formula: —NHCO—; s represents a positive number of 2to 6; t represents a positive number of 1 to 5; and h, which generallyrepresents an average value, represents a positive number of 0 to 30) ora group represented by the formula:

(wherein R¹¹ represents a linear or branched alkyl or alkenyl grouphaving 6 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R¹² represents a hydrogen atom or a methyl group; jrepresents a positive number of 1 to 5; and r, which generallyrepresents an average value, represents a positive number of 0 to 30).

Examples of the tertiary amine salt to be used in the present inventioninclude salts of the above-mentioned organic tertiary amines, forexample, inorganic salts thereof such as hydrochlorides, sulfates andnitrates thereof, and organic salts thereof such as carboxylates andsulfonates thereof.

Examples of the quaternary ammonium salt to be used in the presentinvention include those which will be described below.

(4) Quaternary-ammonium salts represented by the following formula (4):

wherein each A represents an alkylene group having 2 or 3 carbon atoms;R¹ and R² are either the same or different from each other and eachrepresents an alkyl group having 1 to 5 carbon atoms; R³ represents analkyl group having 1 to 5 carbon atoms or a group represented by theformula: (AO)_(j)—H; either i (when R³ is an alkyl group) or the sum ofi and j (when R³ is a group represented by the formula: (AO)_(j)—H),which represents the average oxyalkylene number per molecule, is anumber of 2 to 20; and X⁻ is an appropriate counter anion.

As particular examples of the quaternary ammonium salts represented bythe above formula (4), those represented by the following formula (4′)may be cited:

wherein EO represents an oxyethylene group; PO represents anoxypropylene group; R¹ and R² are either the same or different from eachother and each represents an alkyl group having 1 to 3 carbon atoms; R³represents an alkyl group having 1 to 3 carbon atoms or a grouprepresented by the formula: EO—(PO)_(m)—H; either n (when R³ is an alkylgroup) or the sum of n and m (when R³ is a group represented by theformula: EO—(PO)_(m)—H), which represents the average oxypropylenenumber per molecule, is a number of 2 to 20; and X⁻ is an appropriatecounter anion.

(5) Quaternary ammonium salts represented by the following formula (5):

wherein R¹, R², R³ and R⁴ are either the same or different from oneanother and each represents a hydrogen atom, an alkyl group having 1 to4 carbon atoms or a hydroxyethyl group, or two among R¹, R², R³ and R⁴form a 3- to 7-membered ring together with the nitrogen atom bondedthereto and —O—, —NH— or —NR— (wherein R represents an alkyl grouphaving 1 to 4 carbon atoms) may substitute for one —CH₂— groupconstituting said 3- to 7-membered ring; X⁻ represents an anion ofinorganic or organic, monobasic or polybasic acid; and n represents 1, 2or 3 depending on the valence of X⁻.

(6) Quaternary ammonium salts represented by the following formula (6):

wherein R₁ represents a linear or branched alkyl or alkenyl group having20 to 40 carbon atoms, an alkyl(or alkenyl)arylpolyoxyalkylene, alkyl(oralkenyl)polyoxyethylene or alkyl(or alkenyl)polyoxypropylene grouphaving a linear or branched alkyl or alkenyl group having 20 to 40carbon atoms, or an acylaminoalkyl or acyloxyalkyl group having a linearor branched acyl group having 20 to 40 carbon atoms; R₂ and R₃ areeither the same or different from each other and each represents a grouprepresented by the formula:

a benzyl group, an alkyl group having 1 to 4 carbon atoms or ahydroxyalkyl group having 2 to 4 carbon atoms; R₄ represents an alkyl oralkenyl group having 12 to 30 carbon atoms, an alkylpolyoxyalkylene,alkylarylpolyoxyalkylene, alkylpolyoxyethylene or alkylpolyoxypropylenegroup having an alkyl group having 12 to 30 carbon atoms, or anacylaminoalkyl or acyloxyalkyl group having an acyl group having 12 to30 carbon atoms; and X⁻ represents a counter anion selected from thegroup consisting of a halide ion, a phosphate group having an alkylmoiety with 1 to 10 carbon atoms, a sulfate group having an alkyl moietywith 1 to 10 carbon atoms and a carboxyl group having an alkyl moietywith 1 to 10 carbon atoms.

(7) Quaternary ammonium salts represented by the following formula (7):

wherein at least one of R₁, R₂ and R₃ is a linear or branched alkyl oralkenyl group having 8 to 30 carbon atoms while the other(s) eachrepresents a methyl group, an ethyl group, a benzyl group, a grouprepresented by the formula:

or a group represented by the formula:

(wherein n is a number of 1 to 5); R₄ represents a methyl group or anethyl group; and X⁻, which represents a counter ion, is an anionicoligomer or polymer having an average molecular weight of 300 to 20,000and having an acid type anionic residue, for example, a naphthalenesulfonic acid/formaldehyde condensate.

(8) Quaternary ammonium salts represented by the following formula (8):

wherein R⁷ and R⁸ are either the same or different from each other andeach represents an alkyl group having 1 to 4 carbon atoms; R⁹ representsa hydrogen atom, a benzyl group or an alkyl group having 1 to 4 carbonatoms, preferably an alkyl group having 1 to 4 carbon atoms; R¹⁰ and R¹¹are either the same or different from each other and each represents alinear or branched alkyl or alkenyl group having 4 to 36 carbon atomswhich may be substituted by a hydroxyl group; each R¹² represents ahydrogen atom or a methyl group; each R¹³ represents a hydrogen atom ora methyl group; j and k are either the same or different from each otherand each represents a positive number of 1 to 5; r and s, whichgenerally each represents an average value, are either the same ordifferent from each other and each represents a number of 0 to 30; andX⁻ is a counter ion.

(9) Quaternary ammonium salts represented by the following formula (9):

wherein R represents a hydrogen atom, a benzyl group or an alkyl grouphaving 1 to 4 carbon atoms which may be substituted by a hydroxyl group,preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atomswhich may be substituted by a hydroxyl group; R^(1′) represents an alkylgroup having 1 to 4 carbon atoms which may be substituted by a hydroxylgroup; R^(2′) represents a linear or branched alkyl group having 1 to 36carbon atoms which may be substituted by a hydroxyl group or a linear orbranched alkenyl group having 2 to 36 carbon atoms which may besubstituted by a hydroxyl group, preferably a linear or branched alkylor alkenyl group having 5 to 36 carbon atoms which may be substituted bya hydroxyl group, a group represented by the formula: —C_(n′)—H_(2n′)—(G^(1′))—R^(4′) (wherein R^(4′) represents a linear or branchedalkyl or alkenyl group having 5 to 36 carbon atoms which may besubstituted by a hydroxyl group; G^(1′) represents a group representedby the formula: —OCO— or a group represented by the formula: —NHCO—; andn′ is a positive number of 2 to 6), a group represented by the formula:

(wherein R^(5′) represents a linear or branched alkyl or alkenyl grouphaving 6 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R^(6′) represents a hydrogen atom or a methyl group; m′ is apositive number of 1 to 5; and p′, which generally represents an averagevalue, is a number of 0 to 30) or a group represented by the formula:

(wherein R^(7′) represents a linear or branched alkyl or alkenyl grouphaving 4 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R^(8′) represents a hydrogen atom or a methyl group; G^(2′)represents a group represented by the formula: —OCO— or a grouprepresented by the formula —NHCO—; i′ is a positive number of 2 to 6; k′is a positive number of 1 to 5; and q′, which generally represents anaverage value, is a number of 0 to 30); R^(3′) represents a grouprepresented by the formula:

(wherein R^(9′) represents a linear or branched alkyl or alkenyl grouphaving 4 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R^(10′) represents a hydrogen atom or a methyl group; G^(3′)represents a group represented by the formula: —OCO— or a grouprepresented by the formula: —NHCO—; s′ is a positive number of 2 to 6;t′ is a positive number of 1 to 5; and h′, which generally represents anaverage value, is a number of 0 to 30), or a group represented by theformula:

(wherein R^(11′) represents a linear or branched alkyl or alkenyl grouphaving 6 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R^(12′) represents a hydrogen atom or a methyl group; j′ isa positive number of 1 to 5; and r′, which generally represents anaverage value, is a number of 0 to 30); and X⁻ is a counter ion.

(10) Quaternary ammonium salts represented by the following formula(10):

wherein R¹⁸ represents a hydrogen atom, a benzyl group or an alkyl grouphaving 1 to 4 carbon atoms which may be substituted by a hydroxyl group,preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atomswhich may be substituted by a hydroxyl group; R¹⁹ represents an alkylgroup having 1 to 4 carbon atoms which may be substituted by a hydroxylgroup; R²⁰ represents a linear or branched alkyl or alkenyl group having6 to 36 carbon atoms which may be substituted by a hydroxyl group; R²¹represents a linear or branched alkyl or alkenyl group having 5 to 36carbon atoms which may be substituted by a hydroxyl group; d is apositive number of 1 to 5; and X⁻ is a counter ion.

(11) Quaternary ammonium salt represented by the following formula (11):

wherein R¹ and R² are either the same or different from each other andeach represents an alkyl group having 1 to 4 carbon atoms, a grouprepresented by the formula:

(wherein each R⁷ represents a hydrogen atom or a methyl group; and m1,which generally represents an average value, is a number of 1 to 30) ora group represented by the formula:

(wherein R¹³ represents a linear or branched alkyl or alkenyl grouphaving 5 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R¹⁴ represents a hydrogen atom or a methyl group; and m2;which generally represents an average value, is a number of 1 to 30); R³represents a hydrogen atom, a benzyl group or an alkyl group having 1 to4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to4 carbon atoms; R⁴ represents a group represented by the formula:

(wherein each R⁸ represents a hydrogen atom or a methyl group; R⁹represents a linear or branched alkyl or alkenyl group having 5 to 36carbon atoms which may be substituted by a hydroxyl group; and q1, whichgenerally represents an average value, is a number of 0 to 30), a grouprepresented by the formula: —NHCOR¹⁰ (wherein R¹⁰ represents a linear orbranched alkyl or alkenyl group having 5 to 36 carbon atoms which may besubstituted by a hydroxyl group) or a group represented by the formula:

(wherein each R¹¹ represents a hydrogen atom or a methyl group; R¹²represents a linear or branched alkyl or alkenyl group having 5 to 36carbon atoms which may be substituted by a hydroxyl group; and q2, whichgenerally represents an average value, is a number of 0 to 30); each R⁵represents a hydrogen atom or a methyl group; R⁶ represents a linear orbranched alkyl or alkenyl group having 5 to 35 carbon atoms which may besubstituted by a hydroxyl group; n, which generally represents anaverage value, is a number of 0 to 30; and X⁻ is a counter ion.

Quaternary ammonium salts represented by the above formula (11)includes, for example, those having an oxyalkylene group(s) and thoserepresented by the following formula (11′):

wherein R^(1′) to R^(3′) are either the same or different from oneanother and each represents an alkyl or hydroxyalkyl group having 1 to 4carbon atoms; R^(4′) represents a group represented by the formula:—OCOR (wherein R represents an alkyl or alkenyl group having 14 to 22carbon atoms); R^(6′) represents an alkyl or alkenyl group having 14 to22 carbon atoms; and X′⁻ is a counter anion derived from a strong acid.

(12) Quaternary ammonium salts represented by the following formula(12):

wherein R₁ and R₂ are either the same or different from each other andeach represents an alkyl group having 1 to 4 carbon atoms or a grouprepresented by the formula:

(wherein R₅ represents an alkyl or alkenyl group having 4 to 22 carbonatoms; and R₆ represents an alkyl or alkenyl group having 2 to 20 carbonatoms), provided that at least one of R₁ and R₂ represents a grouprepresented by the formula:

(wherein R₅ and R₆ each has the same meaning as the one defined above);R₃ and R₄ are either the same or different from each other and eachrepresents an alkyl group having 1 to 4 carbon atoms; and X⁻ is acounter anion.

(13) Quaternary ammonium salts represented by the following formula(13):

wherein at least one of R₁, R₂, and R₃ represents an alkyl or alkenylgroup having 8 to 30 carbon atoms while the other(s) each represents amethyl group, an ethyl group, a benzyl group, a group represented by theformula:

a group represented by the formula: —(CH₂CH₂O)_(n)—H (wherein n, whichgenerally represents an average value, is a number of 1 to 15,preferably an integer of 1 to 15) or a group represented by the formula:

R₄ represents a methyl group, an ethyl group or a group represented bythe formula: —CH₂CH₂OH; and X⁻, which represents a counter anion,represents a phosphate group, a phosphonate group, a sulfonate grouphaving a hydrocarbon moiety with at least 7 carbon atoms, a sulfategroup having a hydrocarbon moiety with at least 7 carbon atoms or ananionic oligomer or copolymer having a degree of polymerization of atleast 3 and having an anionic residue.

(14) Quaternary ammonium salts represented by the formula (14):

wherein at least one of R₁, R₂ and R₃ represents a linear or branchedalkyl or alkenyl group having 8 to 30 carbon atoms while the other(s)each represents a methyl group, an ethyl group, a benzyl group, a grouprepresented by the formula:

a group represented by the formula: —(AO)_(x)—H (wherein each Arepresents an alkylene group, preferably an alkylene group having 2 to 4carbon atoms; and x, which generally represents an average value,represents a number of 1 to 60, preferably an integer of 1 to 60) or agroup represented by the formula:

R₄ represents a methyl group, an ethyl group or a group represented bythe formula: —CH₂CH₂OH; and X⁻, which represents a counter anion,represents a halide ion, a phosphate group, a phosphonate group, asulfonate group having a hydrocarbon moiety with at least 7 carbonatoms, a sulfate group having a hydrocarbon moiety with at least 7carbon atoms or an anionic oligomer or copolymer having a degree ofpolymerization of at least 3 and having an anionic residue.

(15) Quaternary ammonium salts represented by the following formula(15):

wherein R₁ and R₂ are either the same or different from each other andeach represents a linear or branched alkyl or hydroxyalkyl group having1 to 30 carbon atoms or a linear or branched alkenyl group having 2 to30 carbon atoms; A₁O and A₂O each represents an oxyalkylene group having2 to 4 carbon atoms; n and m each represents 0 or a positive number,preferably 0 or a positive integer, provided that the sum of n and m,which generally represents an average value, is a number of 1 to 100;and X⁻ represents a counter ion.

(16) Quaternary ammonium salts represented by the following formula(16):

wherein A represents a hydrogen atom, a group represented by theformula: —CH₂CH₂—CN, a group represented by the formula: —CH₂CH₂COOH, agroup represented by the formula:

a group represented by the formula:

(wherein n is a number of 2 to 9; p, which generally represents anaverage value, is a number of 0 to 30; each R represents a hydrogen atomor a methyl group; and R² represents an alkyl or alkenyl group having 4to 30 carbon atoms), a group represented by the formula:

(wherein m is a number of 2 to 9; and R² has the same meaning as the onedefined above) or a group represented by the formula:

(wherein r is a number of 2 to 6; and m, p, R and R² each has the samemeaning as the one defined above); B, C and D are either the same ordifferent from one another and each represents a hydrogen atom, a methylgroup, an ethyl group, a group represented by the formula:

(wherein R³ represents an alkyl or alkenyl group having 4 to 30 carbonatoms; i is a number of 2 to 6; and j, which generally represents anaverage value, is a number of 1 to 10), a group represented by theformula: —CH₂COOH, a group represented by the formula:—(C_(i)H_(2i)O)_(j)—H (wherein i and j each has the same meaning as theone defined above), a group represented by the formula: —CH₂COO⁻, agroup represented by the formula: —CH₂CH(OH)CH₂SO₃ ⁻ or a benzyl group,provided that when one of B, C and D is a group represented by theformula: —CH₂COO⁻ or a group represented by the formula:—CH₂CH(OH)CH₂SO₃ ⁻, then the others are each a groups other than a grouprepresented by the formula: —CH₂COO⁻ and a group represented by theformula: —CH₂CH(OH)CH₂SO₃ ⁻; R¹ represents an alkyl or alkenyl grouphaving 4 to 30 carbon atoms; and X⁻ is a counter ion, provided that whenone of B, C and D is a group represented by the formula: —CH₂COO⁻ or agroup represented by the formula: —CH₂CH(OH)CH₂SO₃ ⁻, then X⁻ is absenttherefrom.

(17) Quaternary ammonium salts represented by the following formula(17):

wherein Y and Z are either the same or different from each other andeach represents an alkyl or alkenyl group having 6 to 30 carbon atoms, agroup represented by the formula:

(wherein each R⁵ represents a hydrogen atom or a methyl group; R⁶represents an alkyl or alkenyl group having 5 to 29 carbon atoms; n is anumber of 2 to 9; and p, which generally represents an average value, isa number of 0 to 30), a group represented by the formula —C₃H₆NHCOR⁶(wherein R⁶ has the same meaning as the one defined above), a grouprepresented by the formula:

(wherein m is a number of 2 to 9; and n, p, R⁵ and R⁶ each has the samemeaning as the one defined above), a group represented by the formula:—C₃H₆OR⁶ (wherein R⁶ has the same meaning as the one defined above) or agroup represented by the formula: —CH₂CH(OH)CH₂OR⁶ (wherein R⁶ has thesame meaning as the one defined above), provided that Y and Z do notrepresent alkyl or alkenyl groups having 1 to 4 carbon atoms at the sametime; R⁴ represents an alkyl group having 1 to 4 carbon atoms or a grouprepresented by the formula:

(wherein q, which generally represents an average value, is a number of1 to 30; and R⁵ has the same meaning as the one defined above); and X⁻is a counter ion.

(18) Quaternary ammonium salts represented by the following formula(18):

wherein R⁷ and R⁸ are either the same or different from each other andeach represents an alkyl group having 1 to 4 carbon atoms, an alkenylgroup having 2 to 4 carbon atoms or a group represented by the formula:

(wherein each R¹⁰ represents a hydrogen atom or a methyl group; and q,which generally represents an average value, is a number of 1 to 30); R⁹represents an alkyl group having 6 to 36 carbon atoms, a grouprepresented by the formula:

(wherein R¹¹ represents an alkyl group having 5 to 35 carbon atoms; m isa number of 2 to 9; p, which generally represents an average value, is anumber of 0 to 30; and R¹⁰ has the same meaning as the one definedabove), a group represented by the formula: —C_(m)H_(2m)NHCOR¹¹ (whereinm and R¹¹ each has the same meaning as the one defined above) or a grouprepresented by the formula:

(wherein r is a number of 2 to 6; and m, p, R¹⁰ and R¹¹ each has thesame meaning as the one defined above); W represents a group representedby the formula:

(wherein p, R¹⁰ and R¹¹ each has the same meaning as the one definedabove), a group represented by the formula: —NHCOR¹¹ (wherein R¹¹ hasthe same meaning as the one defined above) or a group represented by theformula:

(wherein p, r, R¹⁰ and R¹¹ each has the same meaning as the one definedabove); n is a number of 2 to 9; and X⁻ is a counter ion.

Unless otherwise noted with respect to the counter ions (such as X⁻) inthe above quaternary ammonium salts, they are not particularlyrestricted. Examples thereof include halide ions such as Cl⁻, Br⁻ andI⁻, alkyl sulfate (RSO₄ ⁻) groups, alkylbenzenesulfonate (R-benzene-SO₃⁻) groups, alkylnaphthalenesulfonate (R-naphthalene-SO₃ ⁻) groups, fattyacid residues (RCOO⁻), alkyl phosphate (ROPO₃H⁻, wherein R represents analkyl group) groups, anionic oligomers and anionic polymers.

The above compounds can be also classified in the following manner:

(I) compounds represented by the formulae (1), (4), (5), (6), (7), (12),(13), (14) and (15);

(II) compounds represented by the formulae (2), (3), (8), (9) and (10),and compounds represented by the formula (11) excepting thoserepresented by the formula (11′);

(III) compounds represented by the formula (11′) and

(IV) compounds represented by the formulae (16), (17) and (18).

In the present invention, compounds represented by the formulae (6),(7), (12), (13), (14) and (15) are preferably used, compoundsrepresented by the formulae (16), (17) and (18) are still morepreferably used, and compounds represented by the formulae (2), (3),(8), (9), (10) and (11) are most preferably used.

It is needless to say that any desired tertiary amines, tertiary aminesalts and quaternary ammonium salts other than those cited above can beused in the present invention.

[II] Chelating Agent (B)

The chelating agent to be used in the present invention is notparticularly restricted, so long as it is capable of chelating a metalion. Examples of the chelating agent usable in the present inventioninclude amino polycarboxylic acid chelating agents, aromatic oraliphatic carboxylic acid chelating agents, amino acid chelating agents,ether polycarboxylic acid chelating agents, phosphonic acid chelatingagents such as iminodimethylphosphonic acid (IDP) and alkyldiphosphonicacid (ADPA), hydroxy carboxylic acid chelating agents, electrolytechelating agents of polymer (including oligomer) type, anddimethylglyoxime (DG). These chelating agents may be in the form ofeither an acid or a salt such as sodium salt, potassium salt andammonium salt. Alternatively, these chelating agents may be in the formof an ester derivative thereof which can be hydrolyzed.

Examples of the aminopolycarboxylic acid chelating agents include

a) compounds represented by the chemical formula of RNX₂,

b) compounds represented by the chemical formula of NX₃,

c) compounds represented by the chemical formula of R—NX—CH₂CH₂—NX—R,

d) compounds represented by the chemical formula of R—NX—CH₂CH₂—NX₂,

e) compounds represented by the chemical formula of X₂N—R′—NX₂ and

f) compounds similar to compounds of e) and containing four or more Xs,for example, a compound represented by the formula:

In the above formulae, X represents a group represented by the formula:—CH₂COOH or a group represented by the formula: —CH₂CH₂COOH, Rrepresents a group to be contained in these type, known chelating agentssuch as a hydrogen atom, an alkyl group, a hydroxyl group and ahydroxyalkyl group, and R′ represents a group to be contained in thesetype, known chelating agents such as an alkylene group and acycloalkylene group.

Representative examples of the aminopolycarboxylic acid chelating agentsinclude ethylenediaminetetraacetic acid (EDTA),cyclohexanediaminetetraacetic acid (CDTA), nitrilotriacetic acid (NTA),iminodiacetic acid (IDA), N-(2-hydroxyethyl)iminodiacetic acid (HIMDA),diethylenetriaminepentaacetic acid (DTPA),N-(2-hydroxyethyl)ethylenediaminetriacetic acid (EDTA-OH) andglycoletherdiaminetetraacetic acid (GEDTA), and salts thereof.

Examples of the aromatic or aliphatic carboxylic acid chelating agentsto be used in the present invention include oxalic acid, succinic acid,pyruvic acid, salicylic acid and anthranilic acid, and salts, methylesters and ethyl esters thereof. Further, examples of the amino acidchelating agents to be used in the present invention include glycine,serine, alanine, lysine, cystine, cysteine, ethionine, tyrosine andmethionine, and salts and derivatives thereof.

Furthermore, examples of the ether polycarboxylic acid chelating agentsto be used in the present invention include compounds represented by thefollowing formula, compounds similar to the compounds represented by thefollowing formula and salts (e.g., sodium salt) thereof:

wherein Y¹ represents a hydrogen atom, a group represented by theformula: —CH₂COOH or a group represented by the formula: —COOH, and Z¹represents a hydrogen atom, a group represented by the formula: —CH₂COOHor a group represented by the formula:

Examples of the hydroxy carboxylic acid chelating agents to be used inthe present invention include malic acid, citric acid, glycolic acid,gluconic acid, heptonic acid, tartaric acid, lactic acid and saltsthereof.

Examples of the electrolyte chelating agents of polymer (includingoligomer) type to be used in the present invention include acrylic acidpolymers, maleic anhydride polymers, α-hydroxyacrylic acid polymers,itaconic acid polymers, copolymers comprising at least two of theconstituting monomers of these polymers and epoxysuccinic acid polymers.

In addition, chelating agents to be used in the present invenitonfurther include ascorbic acid and thioglycollic acid, and salts thereof.

Among the above-mentioned chelating agents, preferable ones includealiphatic carboxylic acid chelating agents, aromatic carboxylic acidchelating agents, hydroxy carboxylic acid chelating agents, amino acidchelating agents, ether polycarboxylic acid chelating agents, phosphonicacid chelating agents, electrolyte chelating agents of polymer(including oligomer) type, dimethylglyoxime (DG), ascorbic acid andthioglycollic acid, and salts of ascorbic acid and thioglycollic acid.Among them, aliphatic carboxylic acid chelating agents, aromaticcarboxylic acid chelating agents, hydroxy carboxylic acid chelatingagents, amino acid chelating agents and ether polycarboxylic acidchelating agents are still more preferable.

In the present invention, such a chelating agent is used in an amount offrom 0.01 to 30 mol, preferably from 0.05 to 20 mol and still morepreferably from 0.1 to 15 mol, per mol of the above-mentionednitrogen-containing compound (the total content by mol, when two or morenitrogen-containing compounds are used).

It has been a practice to add a small amount of a chelating agent to asurfactant by which the efficacy of an agricultural chemical can beenhanced [see Japanese Patent Publication-A Nos. 2-295907 (published onDec. 6, 1990) and 4-502618 (published on May 14, 1992), and EuropeanPatent Publication-A No. 36106]. In these cases, however, the additionof the chelating agent aims mainly at trapping substances which arecontained in the water for diluting the agricultural chemical andinhibit the activity of the agricultural chemical, namely, trace metalions (e.g., Ca⁺⁺, Mg⁺⁺) to thereby soften hard water. Therefore,chelating agents are used in the prior art only in a small amount. Incontrast, a chelating agent is used in a large amount in the presentinvention compared with the conventional cases. The present inventorshave found for the first time that the efficacy of an agriculturalchemical can be remarkably enhanced by using a chelating agent in alarger amount than the conventional dose together with theabove-mentioned nitrogen-containing compound.

[III] Enhancer Composition for Agricultural Chemicals

The enhancer composition for agricultural chemicals of the presentinvention comprises the above-mentioned nitrogen-containing compound (A)and the chelating agent (B). When used in combination with anagricultural chemical, this enhancer composition for agriculturalchemicals can enhance the efficacy of the agricultural chemical twice tothrice without causing any phytotoxicity. Namely, the enhancer foragricultural chemicals of the present invention can be safely applied tovarious crops without causing any phytotoxicity.

Although the mechanism of action of the enhancer composition foragricultural chemicals of the present invention has not been necessarilyclarified, it is considered as follows. The nitrogen-containingcompounds employed in the present invention are those positively chargedin water. Therefore, it specifically adheres to cell membranes ofplants, microorganisms and insects, invades the membranes and thenabnormally elevates the flowability of the cell membranes, thus causinga disturbance in the membrane functions. As a result, the amount of theagricultural chemical incorporated into the cells is increased and thusthe efficacy of the agricultural chemical is enhanced. It is estimatedthat the chelating agent undergoes some interaction with thenitrogen-containing compound to thereby enhance the efficacy of theagricultural chemical. Accordingly, it seems that the effect of thechelating agent in the present invention essentially differs from theeffect, which has hitherto been lectured, of a chelating agent oftrapping trace metal ions in water and thus enhancing the efficacy of anagricultural chemical. It has been observed in practice that the effectof a nitrogen-containing compound according to the present invention inenhancing the efficacy of an agricultural chemical is strengthened byadding a chelating agent both in distilled water and in hard water.

In the enhancer composition for agricultural chemicals of the presentinvention, the dose of the above-mentioned nitrogen-containing compound(A) can be reduced while maintaining the enhancing effect thereof on anagricultural chemical by further using a surfactant (C) other than thenitrogen-containing compounds (A) and/or an adjuvant for penetration ofagricultural chemicals (D) therewith.

Examples of the surfactant (C) other than the nitrogen-containingcompounds include nonionic surfactants, anionic surfactants andamphoteric surfactants. These surfactants may be used either alone or asa mixture of two or more of them.

Examples of the nonionic surfactants include polyoxyethylene alkylethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkylarylether/formaldehyde condensates, polyoxyalkylene aryl ethers,polyoxyalkylene alkyl esters, polyoxyalkylene alkylsorbitol esters,polyoxyalkylene sorbitan esters, polyoxyalkylene alkylglycerol esters,polyoxyalkylene block copolymers, polyoxyalkylene blockcopolymer/alkylglycerol esters, polyoxyalkylene alkylsulfonamides,polyoxyalkylene rosin esters, polyoxypropylene block copolymers,polyoxyethylene oleyl ethers, polyoxyalkylene alkylphenols,alkylglycosides, alkylpolyglycosides, polyoxyalkylenealkylpolyglycosides, and mixtures comprising two or more of thesesurfactants.

Among anionic surfactants, typical ones are available in the form of anaqueous solution or a solid. Examples thereof include sodium mono- anddialkylnaphthalenesulfonates, sodium α-olefinsulfonate, sodiumalkanesulfonates, alkylsulfosuccinates, alkylsulfates, polyoxyalkylenealkyl ether sulfates, polyoxyalkylene alkyl aryl ether sulfates,polyoxyalkylene styryl phenyl ether sulfates, mono- anddialkylbenzenesulfonates, alkylnaphthalenesulfonates,alkylnaphthalenesulfonate/formaldehyde condensates, alkyl diphenyl ethersulfonates, olefinic sulfonates, mono- and dialkylphosphates,polyoxyalkylene mono- and dialkylphosphates, polyoxyalkylene mono- anddiphenyl ether phosphates, polyoxyalkylene mono- and dialkyl phenylether phosphates, polycarboxylic acid salts, linear and branched alkylpolyoxyalkylene ether acetic acids and salts thereof, linear andbranched alkenyl polyoxyalkylene ether acetic acids and salts thereof,fatty acids and salts thereof, e.g., stearic acid and its salts, oleicacid and its salts, caprylic acid and its salts, capric acid and itssalts and lauric acid and its salts, N-methyl fatty acid taurides andmixtures comprising two or more of these surfactants (including sodium,potassium, ammonium and amine salts).

Examples of suitable ampholytic surfactants include lauryldimethylamineoxide, Armox C/12, amine oxides, Monaterics, Miranols, betaines,Lonzaines, other amine oxides and mixtures thereof.

Among these surfactants, nonionic surfactants, anionic surfactants andmixtures of a nonionic surfactant and an anionic surfactants arepreferable, and mixtures of a nonionic surfactant and an anionicsurfactants are still more preferable. Among these mixtures, those inwhich the weight ratio of the nonionic surfactant to the anionicsurfactant ranges from 1/50 to 50/1 are desired, and those in which theweight ratio ranges from 1/30 to 15/1 are particularly desired.

Among nonionic surfactants, those of the ester type, such aspolyoxyalkylene sorbitan esters and polyoxyalkylene alkyl glycerolesters, polyoxyalkylene alkyl ethers and polyoxyalkylene alkylphenylethers are preferred, and those of the ester type are particularlypreferred from the point of view of environmental conservation, sincethey are excellent in biodegradability. Among anionic surfactants,polyoxyalkylene alkyl ether sulfates, alkylbenzenesulfonates, and linearand branched alkyl polyoxyalkylene ether acetic acids and salts thereofare preferred and polyoxyalkylene alkyl ether sulfates and linear andbranched alkyl polyoxyalkylene ether acetic acids and salts thereof areparticularly preferred.

In the enhancer composition for agricultural chemicals comprising anitrogen-containing compound (A), a chelating agent (B) and a surfactant(C) other than the nitrogen-containing compounds according to thepresent invention, the weight ratio of the nitrogen-containing compound(A) to the surfactant (C) other than the nitrogen-containing compoundspreferably ranges from 1/10 to 50/1, still more preferably from 1/1 to10/1.

The adjuvant for penetration of agricultural chemicals (D) is used forthe efficient penetration of an agricultural chemical into insects,plants, fungi, etc. Examples thereof include those described below.

1) Water including deionized water, aqueous solutions of organic orinorganic acids and aqueous solutions of alkalis.

2) Monohydric alcohols such as methanol, ethanol, n-propanol,isopropanol, n-butanol, isobutanol, isoamyl alcohol, 3-pentanol,n-hexanol, n-heptanol, 2-heptanol, n-octanol, 2-ethylhexanol, n-decanol,undecanol, n-dodecanol, tetradecanol, heptadecanol, cyclohexanol andbenzyl alcohol.

3) Polyhydric alcohols and alcohol ethers such as ethylene glycol,ethylene glycol monomethyl ether, ethylene glycol monomethyl acetate,ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethyleneglycol monoethyl ether acetate, ethylene glycol isopropyl ether,ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethyleneglycol monobutyl ether acetate, ethylene glycol isoamyl ether, ethyleneglycol monophenyl ether, ethylene glycol monophenyl ether acetate,ethylene glycol benzyl ether, ethylene glycol monohexyl ether,dimethoxyethanol, ethylene glycol monoacetate, ethylene glycoldiacetate, diethylene glycol, 1,3-butylene glycol, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, diethylene glycol dimethyl ether, diethylene glycolmethyl ethyl ether, diethylene glycol diethyl ether, diethylene glycoldibutyl ether, triethylene glycol, triethylene glycol monomethyl ether,propylene glycol, propylene glycol monomethyl ether, propylene glycolmonoethyl ether, propylene glycol monobutyl ether, dipropylene glycolmonomethyl ether, dipropylene glycol monoethyl ether, butanediol,2-methyl-2,4-pentanediol, glycerol, glyceryl monoacetate, glycerylmonobutyrate, trimethylolpropane, liquid (at ordinary temperatures)polyethylene glycol, liquid (at ordinary temperatures) polypropyleneglycol and polyvinyl alcohol. Among them, preferable ones arepolyalkylene glycol monoalkyl ethers and polyalkylene glycol dialkylethers, and still more preferable ones are diethylene glycolmonoalkyl(C₁₋₆)ethers, diethylene glycol dialkyl(C₁₋₆)ethers,triethylene glycol monoalkyl(C₁₋₆)ethers and triethylene glycoldialkyl(C₁₋₆)ethers.

4) Halogenated hydrocarbons such as chloroform, carbon tetrachloride,dichloromethane, dichloroethane, trichlorofluoromethane anddichlorodifluoromethane.

5) Ethers such as diethyl ether, diisopropyl ether, dibutyl ether,dihexyl ether, diisoamyl ether, methyl phenyl ether, ethyl phenyl ether,amyl phenyl ether, ethyl benzyl ether, 1,4-dioxane, tetrahydrofuran,tetrahydropyran and polyoxyalkylene phenyl ethers. Among them,preferable ones are polyoxyalkylene phenyl ethers, and still morepreferable ones are polyoxyethylene phenyl ethers wherein the number ofoxyethylene groups per molecule is from 1 to 10.

6) Ketones such as acetone, methylacetone, methyl ethyl ketone, methyln-butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethylketone, acetone oil, acetonylacetone, phorone, isophorone,cyclohexanone, methylcyclohexanone and pyrrolidone.

7) Esters such as methyl acetate, ethyl acetate, n-butyl acetate, n-amylacetate, isoamyl acetate, methylisoamyl acetate, methyl propionate,isoamyl propionate, n-butyl butyrate, butyl stearate, amyl stearate,2-ethylhexyl oleate, lauryl oleate, oleyl oleate, methyl lactate, ethyllactate, ethyl benzoate, propyl benzoate, isoamyl benzoate, benzylabietate, diethyl oxalate, dibutyl oxalate, dimethyl malonate, dimethylphthalate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexylphthalate and alkyl trimellitates (e.g., 2-ethylhexyl trimellitate).Among them, preferable ones are alkyl oleates, alkenyl oleates, alkylphthalates and alkyl trimellitates, and still more preferable ones arealkyl(C₁₋₁₂)oleates and alkenyl(C₂₋₁₂)oleates.

8) Nitrogen-containing compounds such as formamide,N,N-dimethylformamide, acetonitrile and morpholine.

9) Hydrocarbon compounds such as n-pentane, n-hexane, isohexane,n-heptane, n-octane, n-decane, petroleum ether, petroleum benzine,petroleum fractions (e.g., paraffins, kerosine and gas oil),cyclohexane, toluene, xylene, ethylbenzene, chlorobenzene, cumene,methylnaphthalene and dimethyl sulfoxide.

10) Vegetable oils such as soybean oil and cottonseed oil.

Among these adjuvant for penetrations, polyalkylene glycol monoalkylethers and polyalkylene glycol dialkyl ethers are most preferable.

In the enhancer composition for agricultural chemicals comprising anitrogen-containing compound (A), a chelating agent (B) and an adjuvantfor penetration (D) according to the present invention, the weight ratioof the nitrogen-containing compound (A) to the adjuvant, for penetration(D) preferably ranges from 1/5 to 5/1, still more preferably from 1/2 to2/1. When the ratio exceeds 5/1, the enhancing effect of the adjuvantfor penetration (D) is unsatisfactory in contrast, when the ratio islower than 1/5, the enhancing effect of the adjuvant for penetration (D)is no longer improved and, unfavorably, the combination use of theenhancer composition for agricultural chemicals comprising anitrogen-containing compound (A), a chelating agent (B) and an adjuvantfor penetration (D) according to the present invention with aninsecticide or a miticide may cause a serious phytotoxicity to plants.

[IV] Agricultural Chemical Composition

The agricultural chemical composition of the present invention comprisesthe above-mentioned enhancer composition for agricultural chemicals ofthe present invention and an agricultural chemical. In thisspecification, the term “agricultural chemical” means one which isemployed as an active or principle ingredient in common agriculturalchemical compositions or preparations. The enhancer composition foragricultural chemicals of the present invention, which is employed forpreparing the agricultural chemical composition of the presentinvention, may further comprises a surfactant (C) other than thenitrogen-containing compounds (A) and/or an adjuvant for penetration (D)as described above.

In the agricultural chemical composition of the present invention, theweight ratio of the sum total of the nitrogen-containing compound (A)and the chelating agent (B) to the agricultural chemical(s) is from 0.05to 50, preferably from 0.05 to 20 and still more preferably from 0.1 to10. When this ratio is below 0.05, any desired effect of enhancing theeffectiveness of the agricultural chemical(s) can not be fully achieved.When this ratio exceeds 50, on the other hand, the enhancing effect isno longer improved.

Next, examples of the agricultural chemicals to be used in theagricultural chemical composition of the present invention will becited, though the agricultural chemicals to be used in the presentinvention is not restricted thereto.

In the case of fungicides (or bactericides), included are Zineb [zincethylenebis(dithiocarbamate)], Maneb [manganeseethylenebis(dithiocarbamate)], Thiram[bis(dimethylthiocarbamoyl)disulfide], Mancozeb [complex of zinc andmanganese ethylenebis(dithiocarbamate)], Polycarbamate [dizincbis(dimethyldithiocarbamate)ethylenebis(dithiocarbamate)], Propineb[polymeric zinc propylenebis(dithiocarbamate)], benzimidazole fungicidessuch as Benomyl [methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate] andThiophanate-methyl [1,2-bis(3-methoxycarbonyl-2-thioureido)benzene];Vinclozolin[3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione],Iprodione[3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide],Procymidone[N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide],Anilazine (Triazine) [2,4-dichloro-6-(2-chloroanilino)-1,3,5-triazine],Triflumizole[(E)-4-chloro-α,α,α-trifluoro-N-(1-imidazol-1-yl-2-propoxyethylidene)toluidine],Metalaxyl [methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate],Bitertanol[all-rac-1-(biphenyl-4-yl-oxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butan-2-ol],Pyrifenox [2′,4′-dichloro-2-(3-pyridyl)acetophenone (EZ)-O-methyloxime],Fenarimol [2,4′-dichloro-α-(pyridin-5-yl)benzhydryl alcohol], Triforine[1,4-bis-(2,2,2-trichloro-1-formamidoethyl)piperazine], Iminoctadineacetate [1,1′-iminiodi(octamethylene)diguanidinium triacetate],organocopper compound (Oxine-copper [copper 8-quinolinolate]),antibiotic bactericides (streptomycin type, tetracycline type, polyoxinstype, blasticidin S, kasugamycin type, validamycin type), Triadimefon[1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone],Isoprothiolane [diisopropyl 1,3-dithiolan-2-ylidene-malonate],Chlorothalonil (Daconil) [tetrachloroisophthalonitrile], Etridiazol(Pansoil) [5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole], Fthalide[4,5,6,7-tetrachlorophthalide], Iprobenfos (Kitazin P)[O,O-diisopropyl-S-benzyl thiophosphate], Edifenphos (Hinosan) [O-ethylS,S-diphenyl dithiophosphate], Probenazole[3-allyloxy-1,2-benzisothiazole-1,1-dioxide], Captan[N-trichloromethylthiotetrahydrophthalimide] and Fosetyl [aluminumtris(ethylphosphonate)].

In the case of insecticides, included are pyrethroid insecticides suchas Fenvalerate [α-cyano-3-phenoxybenzyl2-(4-chlorophenyl)-3-methylbutanoate] and Cyfluthrin (Baythroid)[α-cyano-4-fluoro-3-phenoxyphenylmethyl3-(2,2-dichloroethenyl)-2,2-dimethylcyclcopropanecarboxylate];organophosphorus insecticides such as Dichlorvos (DDVP) [dimethyl2,2-dichlorovinyl phosphate], Fenitrothion (MEP)[O,O-dimethyl-O-(3-methyl-4-nitrophenyl)thiophosphate], Malathion(Malathon) [S-[1,2-bis(ethoxycarbonyl)ethyl]dimethylphosphorothiol-thionate], Dimethoate [dimethylS-(N-methylcarbamoylmethyl)dithiophosphate], Phenthoate (Elsan)[S-[α-(ethoxycarbonyl)benzyl]dimethyl phosphorothiol-thionate] andFenthion (Baycid)[O,O-dimethyl-O-[3-methyl-4-(methylthio)phenyl]thiophosphate]; carbamateinsecticides such as Fenobucarb (Bassa) [O-sec-butylphenylmethylcarbamate], Metolcarb (MTMC) [m-tolyl methylcarbamate], Xylylcarb(Meobal) [3,4-dimethylphenyl N-methylcarbamate] and Carbaryl (NAC)[1-naphthyl N-methylcarbamate]; Methomyl [S-methylN-(methylcarbamoyloxy)thioacetimidate] and Cartap[1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)propane hydrochloride].

Further, in the case of natural insecticides, included are pyrethrinpreparations, which originate from Chrysanthemum cinerariaefolium,rotenone preparations, which originate from Derris which is a shrub ofthe pulse family, and nicotine preparations [containing3-(1-methyl-2-pyrrolidinyl)pyridine sulfate]. In the case of insectgrowth regulators (IGR), included are diflubenzuron[1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea], teflubenzuron[1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)-urea],chlorofluazuron[1-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-3-(2,6-difluorobenzoyl)urea],buprofezin[2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one]and fenoxycarb [ethyl 2-(4-phenoxyphenoxy)ethylcarbamate].

In the case of miticides (or acaricides), included are Pyridaben[2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazin-3(2H)-one],Acricid [2,4-dinitro-6-sec-butylphenyldimethylacrylate], Chloromite[isopropyl 4,4-dichlorobenzylate], Chlorobenzilate (Akar) [ethyl4,4′-dichlorobenzilate], Dicofol (Kelthane)[1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol], Benzoximate (Citrazon)[ethyl-O-benzoyl-3-chloro-2,6-dimethoxybenzohydroximate], Propargite(Omite) [2-(p-tert-butylphenoxy)cyclohexyl 2-propynyl sulfite],Fenbutatin Oxide (Osadan)[hexakis(β,β-dimethylphenylethyl)distannoxane], Hexythiazox[trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidine-3-carboxamide]and Amitraz [3-methyl-1,5-bis(2,4-xylyl)-1,3,5-triazapenta-1,4-diene].

In the case of herbicides, included are acid amide hebicides such asPropanil (DCPA) [3′,4′-dichloropropionanilide] and Alachlor[2-chloro-2′,6′-diethyl-N-(methoxyethyl)acetanilide]; urea herbicidessuch as Diuron (DCMU) [3-(3,4-dichlorophenyl)-1,1-dimethylurea] andLinuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea); dipyridylherbicides such as Paraquat Dichloride(Paraquat)-[1,1′-dimethyl-4,4′-bipyridirium dichloride] and DiquatDibromide (Diquat) [6,7-dihydrodipyrido[1,2-a:2′,1′-c]-pyrazindiiumdibromide]; diazine herbicides such as Bromacil[5-bromo-3-sec-butyl-6-methyluracil]; S-triazine herbicides such asSimazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine] and Simetryn[2,4-bis(ethylamino)-6-methylthio-1,3,5-triazine]; nitrile herbicidessuch as Dichlobeni (DBN) [2,6-dichlorobenzonitrile]; dinitroanilineherbicides such as Trifluralin[α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine]; carbamateherbicides such as Benthiocarb [S-p-chlorobenzyl diethylthiocarbamate]and MCC [methyl 3,4-dichlorocarbanilate]; diphenylether herbicides suchas Nitrofen (NIP) [2,4-dichlorophenyl-p-nitrophenylether]; phenolherbicides such as PCP [pentachlorophenol]; benzoic acid herbicides suchas Dicamba (MDBA) [3,6-dichloro-2-methoxybenzoic acid dimethylaminesalt]; phenoxy herbicides such as 2,4-D [2,4-dichlorophenoxyacetic acidand salts (sodium, amine and ethylether) thereof], and Mapica (MCPCA)[2′-chloro-2-(4-chloro-o-tolyloxy)acetanilide]; organic phosphorusherbicides such as Glyphosate [N-(phosphonomethyl)glycine] and saltsthereof, Bialaphos [sodium salt ofL-2-amino-4-[(hydroxy)(methyl)phosphinoyl]butyryl-L-alanyl-L-alanine)and Glufosinate [ammonium DL-homoalanin-4-yl (methyl)phosphinate], andaliphatic herbicides such as TCA [trichloroacetic acid and saltsthereof].

In the case of plant growth regulators, included are MH (maleichydrazide), Ethephon [2-chloroethylphosphonic acid], UASTA andBialaphos.

In the present invention, it is preferable to use a fungicide, aninsecticide, a miticide or a plant growth regulator as the agriculturalchemical. When a herbicide is used as the agricultural chemical, it ispreferable to use one other than organophosphorus herbicides.

The agricultural chemical composition of the present invention may beformulated into any preparation such as liquid preparations, emulsions,wettable powders, granules, powders and flowables without anylimitation. Accordingly, the agricultural chemical composition of thepresent invention may contain other additives which are selecteddepending on the formulation or preparation, for example, emulsifiers,dispersing agents and carriers.

The agricultural chemical composition according to the present inventionmay further contain a pH regulator, an inorganic salt or a thickener, ifrequired.

Examples of the pH regulators to be used in the present inventioninclude citric acid, phosphoric acid (e.g., pyrophosphoric acid) andgluconic acid, and salts thereof.

Examples of the inorganic acid salts to be used in the present inventioninclude inorganic mineral salts such as clay, talc, bentonite, zeolite,calcium carbonate, diatomaceous earth and white carbon, and inorganicammonium salts such as ammonium sulfate, ammonium nitrate, ammoniumphosphate, ammonium thiocyanate, ammonium chloride and ammoniumsulfamate.

In addition, examples of thickeners to be used in the present inventioninclude natural, semisynthetic and synthetic, water-soluble thickeners.As natural mucilaginous matters, xanthane gum and zanflow, which arederived from microorganism, and pectine, gum arabic and guar gum, whichare derived from plant, are cited. As semisynthetic mucilaginousmatters, methylated, carboxyalkylated and hydroxyalkylated products ofcellulose such as methylcellulose, carboxymethylcellulose andhydroxymethylcellulose, methylated, carboxyalkylated andhydroxyalkylated products of starch derivatives, and sorbitol are cited.Furthermore, polyacrylates, polymaleates, polyvinylpyrrolidone andpentaerythritol/ethyleneoxide adducts are cited as syntheticmucilaginous matters.

The agricultural chemical composition of the present invention mayfurther contain one or more ingredients such as plant growth regulatorsother than those cited above, fertilizers and preservatives.

The agricultural chemical composition of the present invention is usedin order to control fungi (or bacteria), insects, mites (or acarids) andherbs or to regulate the growth of plants.

The agricultural chemical kit according to the present inventioncomprises a container containing the enhancer composition according tothe present invention and another container containing an agriculturalchemical composition. In this case, the enhancer composition maycomprise at least one nitrogen-containing compound (A) selected from thegroup consisting of a tertiary amine, a tertiary amine salt and aquaternary ammonium salt and a chelating agent. The enhancer compositionmay further comprise a surfactant (C) other than the nitrogen-containingcompounds (A) and/or an adjuvant for penetration (D). Alternatively,another agricultural chemical kit according to the present inventioncomprises a container containing at least one nitrogen-containingcompound (A) selected from the group consisting of a tertiary amine, atertiary amine salt and a quaternary ammonium salt and a chelating agent(B), a container containing a surfactant (C) other than thenitrogen-containing compounds (A) and a container containing anagricultural chemical composition. The container containing at least onenitrogen-containing compound (A) and a chelating agent (B) and/or thecontainer containing a surfactant (C) may further contain an adjuvantfor penetration (D). Furthermore, an agricultural chemical kit whichcomprises a container containing at least one nitrogen-containingcompound (A) selected from the group consisting of a tertiary amine, atertiary amine salt and a quaternary ammonium salt and a chelating agent(B), a container containing an adjuvant for penetration (D) and acontainer containing an agricultural chemical composition, and anotheragricultural chemical kit which comprises a container containing atleast one nitrogen-containing compound (A) selected from the groupconsisting of a tertiary amine, a tertiary amine salt and a quaternaryammonium salt and a chelating agent (B), a container containing asurfactant (C) other than the nitrogen-containing compounds (A), acontainer containing an adjuvant for penetration (D) and a containercontaining an agricultural chemical composition, are included in thescope of the present invention.

The “agricultural chemical composition” which is a constituent of thekit is a composition which comprises an agricultural chemical(s), isfree from the nitrogen-containing compound (A) and is in the form of,for example, an emulsion, a liquid or a wettable powder. Theagricultural chemical composition may contain a small amount of thechelating agent (B).

In the agricultural chemical kit according to the present invention, acomposition comprising an agricultural chemical is separated from theenhancer composition for agricultural chemicals comprising anitrogen-containing compound (A) and a chelating agent (B) according tothe present invention. Namely, the agricultural chemical compositionwhich is a constituent of the kit differs from the agricultural chemicalcomposition of the present invention which comprises the enhancercomposition for agricultural chemicals according to the presentinvention and an agricultural chemical(s) in admixture.

Each of contents in these containers is not restricted in their form butappropriately prepared depending on the use and purpose. The material ofthe container is not restricted so long as it is not react with oraffect the content. Examples of the material include plastics, glass,foil, etc.

The enhancer composition according to the present invention is appliedwith an agricultural chemical to a locus which would benefit from suchtreatment, i.e., the application of the enhancer composition and theagricultural chemical. In general, the enhancer composition and theagricultural chemical are used with water or a liquid carrier. As meansfor applying the enhancer composition for agricultural chemicalsaccording to the present invention, (1) one wherein the agriculturalchemical composition of the present invention containing thenitrogen-containing compound (A) and the chelating agent (B) and havinga preparation form is used (if necessary, the agricultural chemicalcomposition is diluted with, for example, tap water), (2) another onewherein the enhancer composition of the present invention is added to anagricultural chemical composition, which has been diluted with water,and (3) another one wherein the enhancer composition of the presentinvention is diluted with water and then an agricultural chemicalcomposition is diluted with the resultant diluted solution of theenhancer composition, are useful. The desired enhancement effect can beachieved by either means.

The agricultural chemical composition of the present invention includesone containing the agricultural chemical in high concentration, thenitrogen-containing compound (A) in high concentration and the chelatingagent (B) in high concentration, and another one containing theagricultural chemical in an appropriate concentration for application,the nitrogen-containing compound (A) in an appropriate concentration forapplication and the chelating agent (B) in an appropriate concentrationfor application. When the former is used, the agricultural chemicalcomposition is diluted with water, etc., for example, just beforeapplying. On the other hand, the agricultural chemical compositions usedin the above cases (2) and (3) include those containing the agriculturalchemical in high concentration and being free from thenitrogen-containing compound (A).

The contents of the agricultural chemical, the nitrogen-containingcompound (A) and the chelating agent (B) in the diluted solution are notlimited. The content of the agricultural chemical in the dilutedsolution depends on, for example, the kind of the agricultural chemicaland its use. While the contents of the nitrogen-containing compound (A)and the chelating agent (B) in the diluted solution depends on, forexample, the kind of the agricultural chemical to be mixed.

The diluted liquid comprising an appropriate amount of an agriculturalchemical, an appropriate amount of the nitrogen-containing compound (A)and an appropriate amount of the chelating agent (B) is applied to, forexample, plants, crops, vegetables, fruits, trees, fruit trees, grasses,weeds or seeds, and, at the same time, to fungi, bacteria, insects,acarids or mites. In other words, the diluted liquid is applied to afarm, a plantation, a fruit garden, an orchard, a flower garden, a lawn,a wood and a forest.

EXAMPLES

The present invention will now be described in more detail withreference to the following Examples which should not be considered tolimit the scope of the present invention.

Example 1

Use was made of the organic tertiary amines and salts thereof and thequaternary ammonium salts as specified in Tables 1 and 2, and thechelating agents and surfactants as specified in Tables 3, 4-1 and 4-2to thereby give various enhancer compositions for agricultural chemicalsas listed in Tables 3, 4-1 and 4-2.

TABLE 1 Compd. no. Organic tertiary amine or its salt 1

2

3

4

5

TABLE 2 Compd. no. Organic quaternary ammonium salt 6

7

8

9

10

11

12

13

TABLE 3 Formulation Compd. (A) Chelating agent (B) (B)/(A) (A)/(B)/(C)no. no. added by mol Surfactant (C) used by wt. Invention 1 1 EDTA-4Na0.50 — 80/20/0 product 2 1 EDTA-4Na 0.38 POE(10) nonylphenyl ether70/10/20 3 1 EDTA-4Na 0.38 POE(20) sorbitan monooleate 70/10/20 4 2IDA-2Na 0.50 — 80/20/0 5 2 IDA-2Na 0.45 POE(9) nonylphenyl ether75/15/10 6 2 DTPA-5Na 0.08 POE(6) lauryl ether 80/10/10 7 3 NTA-3Na 0.45— 80/20/0 8 3 NTA-3Na 0.26 POE(6) sorbitan monolaurate 70/10/20 9 3NTA-3Na 0.26 POE(25) hardened castor oil 70/10/20 10 4 EGTA-4Na 0.25 —80/20/0 11 4 EGTA-4Na 0.21 POE(10) nonylphenyl ether 70/15/15 12 4EGTA-4Na 0.21 POE(10) octylphenyl ether 70/15/15 13 5 DTPA-5Na 0.44 —80/20/0 14 5 DTPA-5Na 0.35 POE(9) nonylphenyl ether 75/15/10 15 5DTPA-5Na 0.35 POE(6) sorbitan monooleate 75/15/10 16 6 CDTA-4Na 0.56 —80/20/0 17 6 CDTA-4Na 0.25 POE(10) oleate 70/10/20 18 6 CDTA-4Na 0.25POE(10) nonylphenyl ether 70/10/20

TABLE 4 Compd. Formulation (A) Chelating agent (B)/(A) (A)/(B)/(C) no.no. (B) added by mol Surfactant (C) used by wt. Invention 19 7 EDTA-4Na0.33 — 80/20/0 product 20 7 EDTA-4Na 0.30 POE(10) oleate 70/15/15 21 7glycine 12.10 *POE(10) nonylphenyl ether    * ** **POE(20) lauryl ethersulfate sodium 60/20/(15/5) 22 8 NTA-3Na 1.00 — 80/20/0 23 8 NTA-3Na0.57 POE(8) oleyl ether 70/10/20 24 8 methionine 2.35 *POE(8) oleylether    * ** **sodium dodecylbenzenesulfonate 60/20/(15/5) 25 9 ETA-OH0.38 — 80/20/0 26 9 ETA-OH 0.29 POE(6) sorbitan monolaurate 70/15/15 279 ETA-OH 0.29 POE(10) nonylphenyl ether 70/15/15 28 10 methionine 0.87 —80/20/0 29 10 methionine 0.54 POE(9) nonylphenyl ether 70/10/20 30 10ETA-OH 0.22 POE(20) sorbitan monooleate 70/10/20 31 11 cysteine 1.70 —80/20/0 32 11 cysteine 0.88 POE(6) lauryl ether 70/10/20 33 11 cysteine2.13 *POE(6) lauryl ether    * ** **POE(20) lauryl ether sulfate sodium60/20/(15/5) 34 12 malic acid 0.82 — 80/20/0 35 12 citric acid 1.72*P0E(6) sorbitan monooleate    * ** **POE(10) lauryl ether 60/12/(2/26)sulfate sodium 36 12 EDTA-4Na 1.06 POE(20) sorbitan 60/30/10 monooleate37 13 sodium 1.67 — 75/25/0 gluconate 38 13 sodium 1.33 POE(15) palm oilfatty 60/14/26 heptonate acid glyceride 39 13 oxalic acid 7.41 — 75/25/040 13 EDTA-4Na 0.88 POE(15) palm oil fatty 50/10/40 acid 41 13 EDTA-4Na0.88 *POE(15) palm oil fatty     * ** acid glyceride 50/10/(10/30)**POE(10) lauryl ether acetate sodium 42 13 EDTA-4Na 0.88 POE(10) laurylether 50/10/40 acetate sodium Comp. 43 6 — — — 100/0/0 product 44 —EDTA-4Na — — 0/100/0

Chemical formulae of the chelating agents (B) listed in Tables 3, 4-1and 4-2 are as follows:

The above-mentioned enhancer compositions listed in Tables 3, 4-1 and4-2 were each dissolved in deionized water to give a 0.05% by weight [assum total of compound (A), chelating agent (B) and surfactant (C)]dilution. With the use of the 0.05% by weight dilution thus obtained,commercially available herbicides, i.e., Karmex wettable powder(containing 78.5% by weight of DCMU as the active ingredient), Herbiaceliquid formulation (containing 20% by weight of Bialaphos as the activeingredient) and Roundup liquid formulation (containing 41% by weight ofisopropylamine salt of Glyphosate as the active ingredient) were eachdiluted 500-fold. Thus three agricultural chemical compositions wereobtained for each enhancer composition for agricultural chemicals.

Fertile soil obtained from a paddy field, gravels (i.e., river sand) anda culture soil available on the market were mixed one another at theweight ratio of 7:2:1. Pots having an inside diameter of 12 cm werefilled with the soil thus obtained. In order to conduct aglasshouse-test, the seeds of crabgrass were sowed in the pots andgerminated. The pots wherein the growth of the crabglass was abnormalwere abandoned to reduce the irregularity among pots. The pots whereincrabgrasses had been grown at a height of about 18 cm were used in thetest. Spray gun (mf. by Iwata Tosoki Kogyo K.K., type RG) was used forthe application of the agricultural chemical compositions to thecrabgrasses. The crabgrasses in the pots were uniformly sprayed witheach of the agricultural chemical compositions at a ratio correspondingto 1000 l/ha (liter per hectare) to evaluate the herbicidal efficacy.

On the tenth day after the application, the above-ground part of thefresh plant was weighed and the result was expressed in a herbicidalratio on the basis of the fresh weight of the above-ground part in theuntreated lot (see the following formula). $\begin{matrix}{Herbicidal} \\{{ratio}\quad (\%)}\end{matrix} = {\frac{\begin{matrix}{{above}\text{-}{ground}} \\{{fresh}\quad {weight}} \\{(g)\quad {of}\quad {an}} \\{{untreated}\quad {lot}}\end{matrix} - \begin{matrix}{{above}\text{-}{ground}} \\{{fresh}\quad {weight}} \\{(g)\quad {of}\quad a} \\{{test}\quad {lot}}\end{matrix}}{\begin{matrix}{{above}\text{-}{ground}\quad {fresh}\quad {weight}} \\{(g)\quad {of}\quad {an}\quad {untreated}\quad {lot}}\end{matrix}} \times 100}$

Tables 5, 6-1 and 6-2 show the herbicidal ratios of the agriculturalchemical compositions.

TABLE 5 Herbicidal ratio (%) Karmex Herbiace Roundup Formulationwettable liquid liquid no. powder formulation formulation Invention 172.1 81.4 85.3 product 2 75.6 82.5 89.4 3 75.6 80.3 88.4 4 80.1 83.986.5 5 83.3 85.8 90.2 6 82.4 89.1 86.3 7 73.1 87.2 82.4 8 77.5 85.6 85.69 72.5 88.9 83.4 10 78.5 85.8 81.5 11 75.4 87.2 84.2 12 78.5 85.8 85.513 80.3 90.1 92.1 14 78.5 89.8 91.5 15 79.1 88.3 93.6 16 74.5 92.4 87.217 77.8 90.5 90.3 18 79.1 91.3 89.4

TABLE 6 Herbicidal ratio (%) Karmex Herbiace Roundup Formulationwettable liquid liquid no. powder formulation formulation Invention 1971.5 78.5 79.6 product 20 73.0 76.7 80.0 21 75.8 80.8 76.7 22 76.9 85.391.0 23 78.1 82.4 87.3 24 77.9 85.3 84.9 25 75.4 81.5 90.3 26 79.3 83.593.5 27 79.2 88.7 92.5 28 73.8 88.8 78.9 29 77.6 87.1 83.5 30 77.6 85.982.8 31 79.8 84.2 80.5 32 80.5 88.2 82.4 33 83.0 86.5 79.8 34 79.6 87.591.4 35 76.3 86.5 90.6 36 80.2 89.2 93.8 37 81.2 84.6 90.6 38 75.4 83.293.0 39 80.3 88.5 95.4 40 70.8 79.6 82.4 41 78.2 84.0 90.4 42 70.2 77.280.2 Comp. 43 53.2 59.4 65.8 product 44 39.8 51.0 54.7 Added none 39.850.6 52.3

Example 2

Female imagines of Tetranychus kanzawai kishida were planted onto kidneybean leaf disks at a ratio of 30 imagines per lot on three runs and thenincubated at 25° C. for 24 hours. Subsequently, the whole leaf diskswere dipped in a test solution for 5 seconds. After taking out of thetest solution and allowing to stand at 25° C. for 48 hours, the leafdisks were observed and the miticidal ratios thereof were determined onthe basis of the result in the untreated lot (refer to the followingequation). $\begin{matrix}{Miticidal} \\{{ratio}\quad (\%)}\end{matrix} = {\frac{\begin{matrix}{{the}\quad {number}\quad {of}} \\{{living}\quad {mites}\quad {of}} \\{{an}\quad {untreated}\quad {lot}}\end{matrix} - \begin{matrix}{{the}\quad {number}\quad {of}} \\{{living}\quad {mites}\quad {of}} \\{a\quad {test}\quad {lot}}\end{matrix}}{\begin{matrix}{\quad {{the}\quad {number}\quad {of}\quad {living}\quad {mites}\quad {of}}\quad} \\{{an}\quad {untreated}\quad {lot}}\end{matrix}} \times 100}$

As miticides, Nissorun V emulsion (containing 55% by weight of activeingredients including 50% by weight of hexythiazox and 5% by weight ofDDVP) and Osadan wettable powder 25 (containing 25% by weight ofphenbutatin oxide as the active ingredient) were each diluted 3,000-foldwith the use of deionized water, and the dilutions thus obtained wereused. The same enhancer compositions for agricultural chemicals as thoseemployed in Example 1 were used. The concentration of each enhancercomposition for agricultural chemicals [i.e., sum total of compound (A),chelating agent (B) and surfactant (C)] in the dilution was adjusted to0.05% by weight. Further, the above procedure was repeated without usingany enhancer compositions. Tables 7, 8-1 and 8-2 show the results.

TABLE 7 Miticidal ratio (%) Osadan Formulation Nissolan V wettable no.emulsion powder 25 Invention 1 78.9 82.2 product 2 83.3 85.6 3 82.2 85.64 80.0 88.9 5 82.2 87.8 6 80.0 85.6 7 85.6 83.3 8 83.3 82.2 9 87.8 84.410 80.0 80.0 11 78.9 80.0 12 80.0 78.9 13 83.3 83.3 14 85.6 82.2 15 84.483.3 16 78.9 75.6 17 78.9 78.9 18 77.8 75.6

TABLE 8 Miticidal ratio (%) Osadan Formulation Nissolan V wettable no.emulsion powder 25 Invention 19 84.4 87.8 product 20 85.6 88.9 21 84.488.9 22 83.3 80.0 23 85.6 82.2 24 82.2 85.6 25 78.9 82.2 26 82.2 83.3 2780.0 80.0 28 86.7 82.2 29 87.8 80.0 30 83.3 83.3 31 77.8 76.7 32 80.078.9 33 80.0 78.9 34 80.0 80.0 35 82.2 80.0 36 86.7 83.3 37 82.2 80.0 3882.2 82.2 39 87.8 86.7 40 70.6 76.2 41 79.2 80.6 42 72.4 72.4 Comp. 4355.6 60.0 product 44 42.2 44.4 Added none 38.9 40.0

Example 3

Rice planthopper larvae of the third instar were incubated and used inan efficacy test on insecticides in triplicate runs by the dippingmethod (each lot having 10 larvae). The insecticidal ratio wasdetermined in the same manner as the one employed for the determinationof the miticidal ratio. Commercially available insecticides, i.e.,Sumithion emulsion (containing 50% by weight of MEP as the activeingredient) and Malathon emulsion (containing 50% by weight of malathonas the active ingredient) were each diluted 3,000-fold with the use ofdeionized water, and the dilutions thus obtained were used. As theenhancer compositions for agricultural chemicals, those employed inExample 1 were used in such a manner as to adjust the concentration ofeach enhancer composition [i.e., sum total of compound (A), chelatingagent (B) and surfactant (C)] in the diluted solution to 0.1% by weight.Tables 9, 10-1 and 10-2 show the results.

TABLE 9 Insecticidal ratio (%) Formulation Sumithion Malathon no.emulsion emulsion Invention 1 76.7 83.3 product 2 80.0 86.7 3 76.7 83.34 80.0 86.7 5 83.3 86.7 6 83.3 90.0 7 80.0 83.3 8 80.0 83.3 9 80.0 86.710 76.7 86.7 11 83.3 83.3 12 83.3 86.7 13 80.0 80.0 14 80.0 83.3 15 83.383.3 16 76.7 83.3 17 76.7 80.0 18 73.3 90.0

TABLE 10 Insecticidal ratio (%) Formulation Sumithion Malathon no.emulsion emulsion Invention 19 86.7 86.7 product 20 90.0 90.0 21 90.090.0 22 80.0 90.0 23 76.7 86.7 24 83.3 86.7 25 90.0 86.7 26 83.3 90.0 2783.3 90.0 28 76.7 83.3 29 80.0 83.3 30 83.3 83.3 31 83.3 80.0 32 80.083.3 33 83.3 80.0 34 76.7 76.7 35 80.0 76.7 36 83.3 80.0 37 80.0 83.3 3883.3 83.3 39 90.0 86.7 40 72.0 75.2 41 79.6 80.0 42 73.2 73.5 Comp. 4356.7 63.3 product 44 46.7 50.0 Added none 40.0 43.3

Example 4

Conidia of Sphaerotheca fuliginea acquiring the resistance againstfungicides were inoculated into young cucumber seedlings at thetrifoliate stage at a ratio of 10⁸ per pot, which were then allowed tostand at 25° C. under a relative humidity of 90% for 2 days in the dark.

Then, a marketed fungicide, i.e., Bayleton wettable powder 5 (containing5% by weight of triadimefon as the active ingredient) was diluted3,000-fold with the 2,500-fold dilution (diluent: deionized water) ofeach of the enhancer compositions employed in Example 1. The dilutionthus obtained was applied onto the seedlings at a ratio of 5 ml per pot.After allowing the pots to stand at 25° C. under a relative humidity of85%, lesions were counted and the preventive value was calculated inaccordance with the following equation. Tables 11,-12-1 and 12-2 showthe results. $\begin{matrix}{Preventive} \\{value}\end{matrix} = {\left\lbrack {1 - \frac{{{no}.\quad {of}}\quad {lesions}\quad {of}\quad a\quad {test}\quad {lot}}{\begin{matrix}{{{no}.\quad {of}}\quad {lesions}\quad {of}} \\{{an}\quad {untreated}\quad {lot}}\end{matrix}\quad}} \right\rbrack \times 100}$

TABLE 11 Preventive value Formulation Bayleton wettable no. powder 5Invention 1 89.5 product 2 92.2 3 93.3 4 92.1 5 95.2 6 94.8 7 85.8 890.4 9 93.5 10 94.0 11 93.0 12 95.4 13 85.3 14 88.9 15 85.3 16 90.5 1792.4 18 93.8

TABLE 12 Preventive value Formulation Bayleton wettable no. powder 5Invention 19 95.2 product 20 100.0 21 100.0 22 91.4 23 87.3 24 89.4 2591.8 26 95.4 27 100.0 28 88.2 29 93.5 30 95.1 31 90.3 32 95.4 33 100.034 92.6 35 95.4 36 100.0 37 82.5 38 83.2 39 90.6 40 80.5 41 85.6 42 78.2Comp. 43 69.8 product 44 57.6 Added none 54.7

The above Examples 1 to 4 show tests whereby the efficacies of theenhancer compositions for agricultural chemicals of the presentinvention were compared with those of common cationic surfactantsemployed as enhancers for agricultural chemicals or chelating agents.

As Tables 5 to 12-2 clearly show, since the chelating agent furtherenhanced the effect of at least one nitrogen-containing compoundselected from the group consisting of a tertiary amine, a tertiary aminesalt and a quaternary ammonium salt in enhancing the efficacy of theagricultural chemicals in the enhancer compositions for agriculturalchemicals of the present invention, the enhancer compositions foragricultural chemicals of the present invention exhibited remarkableeffects of enhancing the efficacy of the agricultural chemicals.

When a chelating agent was used alone, the efficacy of an agriculturalchemical could be somewhat enhanced thereby but the effect could notattain any practically usable level.

Accordingly, it has been found that in the enhancer compositions foragricultural chemicals of the present invention, the chelating agentspecifically enhances the effect of at least one nitrogen-containingcompound selected from the group consisting of a tertiary amine, atertiary amine salt and a quaternary ammonium salt of enhancing theefficacy of the agricultural chemicals.

Example 5

The same test as the one effected in Example 1 was carried out by usingRoundup liquid formulation (containing 41% by weight of activeingredient) as a herbicide, and the formulation Nos. 13, 27 and 32 ofExample 1 as enhancer compositions each in the amount as specified inTable 13. Table 13 shows the results. In Table 13, the term “herbicideconcn.” means the concentration of the marketed herbicide formulation ina dilution to be applied, the term “enhancer compn. concn.” means theconcentration of the enhancer composition [i.e. sum total of compound(A), chelating agent (B) and surfactant (C)] in a dilution to beapplied, and the term, “agricultural chemical” means the activeingredient(s) of the marketed herbicide formulation.

TABLE 13 Agricultural Enhancer chemical/ Formu- Herbicide compn.enhancer Herbicidal Test lation concn. concn. compn. ratio no. no. (ppm)(ppm) (by wt.) (%) 1 Formu- 1000 50  1/0.12 80.5 2 lation 1000 100 1/0.24 87.4 3 no. 13 1000 500 1/1.2 94.0 4 1000 1000 1/2.4 95.8 5 10005000 1/12  94.2 6 1000 10000 1/24  89.2 7 Formu- 1000 50  1/0.12 82.3 8lation 1000 100  1/0.24 90.4 9 no. 27 1000 500 1/1.2 93.5 10 1000 10001/2.4 96.2 11 1000 5000 1/12  96.0 12 1000 10000 1/24  90.5 13 Formu-1000 50  1/0.12 78.4 14 lation 1000 100  1/0.24 80.8 15 no. 32 1000 5001/1.2 84.5 16 1000 1000 1/2.4 88.9 17 1000 5000 1/12  87.8 18 1000 100001/24  88.0 19 — 1000 0 — 55.2

Example 6

The enhancer compositions for agricultural chemicals listed in Table 14were prepared by adding an adjuvant for penetration to each of theenhancer compositions listed in Tables 4-1 and 4-2.

The above-mentioned enhancer compositions for agricultural chemicalslisted in Table 14 were each dissolved in deionized water to give a0.05% by weight [as sum total of compound (A), chelating agent (B) andsurfactant (C)] dilution. With the use of the 0.05% by weight dilutionthus obtained, commercially available herbicides, i.e., Karmex wettablepowder (containing 78.5% by weight of DCMU as the active ingredient),Herbiace liquid formulation (containing 20% by weight of Bialaphos asthe active ingredient) and Roundup liquid formulation (containing 41% byweight of isopropylamine salt of Glyphosate as the active ingredient)were each diluted 700-fold. Thus three agricultural chemicalcompositions were obtained for each enhancer composition foragricultural chemicals.

The same test as the one effected in Example 1 was carried out by usingthe agricultural chemical compositions thus obtained, and theirherbicidal ratios were determined. Table 15 show the results.

TABLE 14 Base Formu- formu- Adjuvant for (A + B + C)/ lation lationpenetration (D) (D) (A)/(B) no. no. added by wt. by wt. Invention 45 22diethylene glycol 1/0.5 1/0.63 product monobutyl ether 46 34 POE(3)phenol 1/0.8 1/1   47 37 2-ethylhexyl 1/0.7 1/0.93 oleate 48 41diethylene glycol 1/1   1/2   monobutyl ether Comp. 49 43 polyethylene1/1   1/1   product glycol (degree of polymerization: 400) 50 44diethylene glycol 1/1   0 monobutyl ether

TABLE 15 Herbicidal ratio (%) Karmex Herbiace Roundup Formulationwettable liquid liquid no. powder formulation formulation Invention 4569.4 74.2 80.4 product 46 68.8 74.0 78.6 47 70.6 76.5 82.1 48 73.2 82.186.3 Comp. 49 45.3 49.8 56.2 product 50 32.4 40.2 43.6 Added none 31.638.4 40.6

The invention being thus described, it will be obvious that the same maybe varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the invention, and all suchmodifications as would be obvious to one skilled in the art are intendedto be included within the scope of the following claims.

What is claimed is:
 1. An agricultural chemical composition, comprising:(a) an agricultural chemical; (b) a nitrogen-containing compound of theformula:

 wherein R¹ and R² are the same or different from each other and eachrepresents an alkyl group having 1 to 4 carbon atoms which may besubstituted by a hydroxyl group; R³ and R⁴ are the same or differentfrom each other and each represents a linear or branched alkyl oralkenyl group having 4 to 36 carbon atoms which may be substituted by ahydroxyl group; each R⁵ represents a hydrogen atom or a methyl group;each R⁶ represents a hydrogen atom or a methyl group; m and n are thesame or different from each other and each represents a positive numberof 1 to 5; and p and q, which each represents an average value, areeither the same or different from each other and each represents anumber of 0 to 30, or an inorganic organic salt thereof; and c) achelating agent selected from the group consisting of aminopolycarboxylic acid chelating agents or salt thereof, aromaticcarboxylic acid chelating agents or salt thereof, a salt of aliphaticcarboxylic acid chelating agents, amino acid chelating agents or saltthereof, ether polycarboxylic acid chelating agents or salt thereof,phosphonic acid chelating agents or salt thereof, a salt of hydroxycarboxylic acid chelating agents, polymer or oligomer electrolytechelating agents, dimethylglyoxime (DG), ascorbic acid or a saltthereof, and thioglycollic acid or a salt thereof; wherein the contentof the chelating agent ranges from 0.01 to 30 mol per mol of thenitrogen-containing compound and the weight ratio of the total of thenitrogen-containing compound and the chelating agent to the agriculturalchemical ranges from 0.05 to
 50. 2. An agricultural chemicalcomposition, comprising: (a) an agricultural chemical; (b) anitrogen-containing compound of the formula:

 wherein R¹ represents an alkyl group having 1 to 4 carbon atoms whichmay be substituted by a hydroxyl group; R² represents a linear orbranched alkyl group having 1 to 36 carbon atoms which may besubstituted by a hydroxyl group or a linear or branched alkenyl grouphaving 2 to 36 carbon atoms which may be substituted by a hydroxylgroup, a group represented by the formula: —CH_(n)H_(2n)—OCO—R⁴ or—C_(n)H_(2n)—NHCO—R⁴ (wherein R⁴ represents a linear or branched alkylor alkenyl group having 5 to 36 carbon atoms which may be substituted bya hydroxyl group; and n represents a positive number of 2 to 6), a grouprepresented by the formula:

(wherein R⁵ represents a linear or branched alkyl or alkenyl grouphaving 6 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R⁶ represents a hydrogen atom or a methyl group; m is apositive number of 1 to 5; and p is a number of 0 to 30) or a grouprepresented by the formula:

 (wherein R⁷ represents a linear or branched alkyl or alkenyl grouphaving 4 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R⁸ represents a hydrogen atom or a methyl group; G²represents a group represented by the formula: —OCO— or a grouprepresented by the formula: —NHCO—; i represents a positive number of 2to 6; k represents a positive number of 1 to 5; and q represents anumber of 0 to 30); and R³ represents a group represented by theformula:

 (wherein R⁹ represents a linear or branched alkyl or alkenyl grouphaving 4 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R¹⁰ represents a hydrogen atom or a methyl group; G³represents a group represented by the formula: —OCO— or a grouprepresented by the formula: —NHCO—; s represents a positive number of 2to 6; t represents a positive number of 1 to 5; and h represents apositive number of 0 to 30) or a group represented by the formula:

 (wherein R¹¹ represents a linear or branched alkyl or alkenyl grouphaving 6 to 36 carbon atoms which may be substituted by a hydroxylgroup; each R¹² represents a hydrogen atom or a methyl group; jrepresents a positive number of 1 to 5; and r represents a positivenumber of 0 to 30) or an inorganic or organic salt thereof; and (c) achelating agent selected from the group consisting of aminopolycarboxylic acid chelating agents or salt thereof, aromaticcarboxylic acid chelating agents or salt thereof, a salt of aliphaticcarboxylic acid chelating agents, amino acid chelating agents or saltthereof, ether polycarboxylic acid chelating agents or salt thereof,phosphonic acid chelating agents or salt thereof, a salt of hydroxycarboxylic acid chelating agents, polymer or oligomer electrolytechelating agents, dimethylglyoxime (DG), ascorbic acid or a saltthereof, and thioglycollic acid or a salt thereof; wherein the contentof the chelating agent ranges from 0.01 to 30 mol per mol of thenitrogen-containing compound and the weight ratio of the total of thenitrogen-containing compound and the chelating agent to the agriculturalchemical ranges from 0.05 to
 50. 3. An agricultural chemicalcomposition, comprising: (a) an agricultural chemical; (b) anitrogen-containing compound of the formula:

wherein R^(1′) to R^(3′) are either the same or different from eachanother and each represents an alkyl or hydroxyalkyl group having 1 to 4carbon atoms, R^(4′) represents a group represented by the formula:—OCOR, wherein R represents an alkyl or alkenyl group having 14 to 22carbon atoms, R^(6′) represents an alkyl or alkenyl group having 14 to22 carbon atoms, and X⁻ is a counter ion derived from a strong acid; and(c) a chelating agent selected from the group consisting of aminopolycarboxylic acid chelating agents or salt thereof, aromaticcarboxylic acid chelating agents or salt thereof, a salt of aliphaticcarboxylic acid chelating agents, amino acid chelating agents or saltthereof, ether polycarboxylic acid chelating agents or salt thereof,phosphonic acid chelating agents or salt thereof, a salt of hydroxycarboxylic acid chelating agents, polymer or oligomer electrolytechelating agents, dimethylglyoxime (DG), ascorbic acid or a saltthereof, and thioglycollic acid or a salt thereof; wherein the contentof the chelating agent ranges from 0.01 to 30 mol per mol of thenitrogen-containing compound and the weight ratio of the total of thenitrogen-containing compound and the chelating agent to the agriculturalchemical ranges from 0.05 to
 50. 4. The agricultural chemicalcomposition according to claim 1, 2 or 3, wherein said agriculturalchemical composition further comprises a surfactant other than saidnitrogen-containing compound.
 5. The agricultural chemical compositionof claim 4, wherein the weight ratio of the nitrogen-containing compoundto the surfactant other than the nitrogen-containing compound rangesfrom 1/10 to 50/1.
 6. The agricultural chemical composition of claim 1,2 or 3, wherein said agricultural chemical composition further comprisesan adjuvant for penetration of agricultural chemicals.
 7. Theagricultural chemical composition of claim 6, wherein the weight ratioof the nitrogen-containing compound to the adjuvant ranges from 1/5 to5/1.
 8. The composition according to claim 3, wherein the counter ion X⁻is a halide, acetate, methyl sulfate, ethylsulfate, a phosphate group, aphosphonate group, a sulfonate group having a hydrocarbon moiety with atleast 7 carbon atoms, a sulfate group having a hydrocarbon moiety withat least 7 carbon atoms, or an anionic oligomer or copolymer having adegree of polymerization of at least 3 and having an anionic residue, ananionic oligomer or polymer having an average molecular weight of 300 to20,000 and having an acidic anionic residue.
 9. The compositionaccording to claim 1, 2 or 3, wherein said agricultural chemicalcomposition further comprises an ingredient selected from the groupconsisting of a pH regulator, an inorganic salt, a thickener, a plantgrowth regulator, fertilizer and a preservative.